EP0172362B1 - Cold-curable pur dispersions, their production and their use - Google Patents

Cold-curable pur dispersions, their production and their use Download PDF

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Publication number
EP0172362B1
EP0172362B1 EP85107926A EP85107926A EP0172362B1 EP 0172362 B1 EP0172362 B1 EP 0172362B1 EP 85107926 A EP85107926 A EP 85107926A EP 85107926 A EP85107926 A EP 85107926A EP 0172362 B1 EP0172362 B1 EP 0172362B1
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Prior art keywords
prepolymer
carbon atoms
dispersion
formaldehyde
water
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EP85107926A
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German (de)
French (fr)
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EP0172362A1 (en
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Josef Dr. Disteldorf
Hans-Jürgen Haage
Horst Dr. Schnurbusch
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Huels AG
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Huels AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/83—Chemically modified polymers
    • C08G18/84—Chemically modified polymers by aldehydes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step

Definitions

  • the invention relates to cold-curing anionic PU dispersions which are suitable for coating surfaces, producing films, sealants and leather finishes.
  • Emulsifier-free ionomer dispersions based on polyurethanes have proven themselves in practice. The reason for this is likely to be their high mechanical and chemical stability, their exceptional film-forming ability, their good adhesion to surfaces and their great variability in terms of composition and desired properties.
  • Such PU dispersions are usually produced in this way: a prepolymer is produced from a polyisocyanate and a polyol which is used in less than the stoichiometric amount. This is reacted with an ionomeric compound which gives the prepolymer self-emulsifying properties. A dispersion is prepared, chain extension is carried out and the solvent is removed by the so-called “acetone” method (cf. Die Angewandte Makromolekulare Chemie 98, 133-165 (1981).
  • the remaining free NCO groups of the prepolymer are used to react with a chain extender.
  • linear anionic prepolymers are extended with diamines and then with a crosslinking agent such as. B. a methoxymethylated melamine or urea at temperatures above 150 ° C and crosslinked. There is therefore no crosslinking at room temperature. However, this is desirable since many substrates are not thermally stable.
  • the dispersions of the German published specification 26 24 442 are obtained as follows: First, a prepolymer is produced which, in addition to free NCO groups, also has anionic salt groups and has a viscosity of 50 to 10,000 mPa ⁇ s. This is then reacted with compounds whose active hydrogens react faster with the NCO groups than water. Suitable compounds are ammonia, primary and secondary amines, preferably diamines, hydrazine derivatives (column 13, line 35 ff.), Hydrazides of dicarboxylic acids and sulfonic acids, such as, for example, adipic acid mono- and dihydrazide (column 14, line 13 ff.).
  • a prepolymer with a linear molecular structure is preferably used.
  • the at least 70 percent by weight solution of the prepolymer should preferably have a maximum viscosity of 10,000 mPa. have sec.
  • the free NCO groups of the ionomer are chain-extended with the amino groups of the diaminohydrazide.
  • the final crosslinking takes place through the reaction known per se between formaldehyde and the hydrazide groups.
  • This invention therefore relates to the processes for the production of aqueous PUR dispersions according to claims 1 to 3, the dispersions obtained by these processes according to claim 4 and the use of the dispersions for the production of films according to claim 5.
  • the process according to the invention is based on the knowledge that dicarboxylic acid hydrazides, such as adipic acid dihydrazide, are not very suitable for crosslinking the prepolymer.
  • dicarboxylic acid hydrazides such as adipic acid dihydrazide
  • Our own investigations showed that the reactivity of the hydrazide groups towards the free NCO groups of an ionomer based on isophorone diisocyanate obtained according to Example 4.1 is so low that the reaction with water becomes a serious side reaction (cf. Table 1). Similar results were obtained with ionomers based on other isocyanates.
  • the water reaction is undesirable because it makes no contribution to branching.
  • the reaction of the prepolymer with a dihydrazide also has an unfavorable effect.
  • it is not only the desired reaction of a hydrazide group with the prepolymer; rather, the reaction of both functional groups can be expected to a considerable extent.
  • the number of hydrazide groups bound to the prepolymer, which are available for the final crosslinking with formaldehyde is severely limited.
  • a prepolymer is made from a polyisocyanate, a polyol and an anionic compound.
  • the solvent used is preferably N-methylpyrrolidone and / or acetone.
  • Dibutyltin dilaurate (DBTL) can be added as a catalyst.
  • Carbon and sulfonic acids with a maximum of 10 carbon atoms are used as anionic compounds.
  • Diaminocarboxylic acids, diaminosulfonic acids and dihydroxycarboxylic acids are suitable.
  • Dimethylolpropionic acid is preferred.
  • the free acid groups of the prepolymer are then neutralized by adding a base.
  • This can be, for example, an alkali hydroxide or a tertiary amine. Triethylamine is preferred.
  • the neutralized prepolymer is not stable in storage. It should therefore be processed soon.
  • the aqueous dispersion is preferably produced by setting a vigorous stirring speed (approx. 100 revolutions per minute) and adding one to three times the amount of water.
  • an approximately 30% strength aqueous solution of the diaminohydrazide of the formula I is preferably rapidly run into the resulting dispersion with stirring.
  • a dilute formalin solution is preferably added at a temperature of about 45 ° C. and the mixture is reacted at this temperature for about 30 minutes until the methylol has completely formed.
  • the diaminohydrazide I is obtained by reacting a diamine of the formula H 2 NR-NH 2 with 0.2 to 2 mol of an acrylic acid derivative, preferably ethyl acrylate, and subsequently with hydrazine.
  • Suitable diamines of the formula H 2 NR-NH 2 are aliphatic diamines with 2 to 15 C atoms or cycloaliphatic or aromatic diamines each with 6 to 15 C atoms, such as.
  • Isophoronediamine is preferred.
  • the finished dispersions are e.g. B. applied with a squeegee to a smooth surface (e.g. glass or metal).
  • a smooth surface e.g. glass or metal.
  • Dimethylolpropionic acid optionally trimethylolpropane and N-methylpyrrolidone and / or acetone are placed in a three-necked flask and heated to 60 ° C. with gentle stirring. Now the polyol and dibutyltin dilaurate are stirred in. The required amount of IPDI is added so that the reaction temperature does not exceed 80 ° C. After a reaction time of about 5 hours, when the respective theoretical NCO number has been reached, the mixture is allowed to cool. Triethylamine is added until the reaction mixture has a neutral reaction, the stirring speed is set at 100 revolutions per minute and the water is added within 1 minute.
  • a 30% aqueous solution of the hydrazide according to Example 1 is added within 1 minute. It is important to ensure that the aqueous solution can flow directly into the resulting dispersion without touching the inner wall of the reaction flask. After 5 minutes the stirring speed is reduced. The reaction solution is kept at 45 ° C. for 2 hours, the 37% aqueous formalin solution is added and the mixture is kept at 45 ° C. for a further hour. After cooling, the reaction solution is filtered through a filter cloth. If acetone is used as the solvent, it is drawn off at a maximum temperature of 60 ° C. in a rotary evaporator under reduced pressure. The dispersions obtained have a solids content of about 30 percent by weight.
  • a linear polyester with an OH number of 110 is prepared from 4 moles of adipic acid, 3 moles of neopentyl glycol and 2 moles of 1,6-hexanediol.
  • a polytetramethylene glycol with a molecular weight of 1,000 is used.
  • Such a product is commercially available under the name TERATHANE® 1,000 (manufacturer E.I. du Pont de Nemours and Company, Wilmington, Del., USA).
  • a polytetramethylene glycol with a molecular weight of 2000 is used.
  • Such a product is commercially available under the name TERATHANE® 2000 (manufacturer E.I. du Pont de Nemours and Company, Wilmington, Del., USA).
  • a polycaprolactone with a molecular weight of 2000 is used.
  • Such a product is commercially available under the name CAPA® 220 (manufacturer Solvay & Cie., B-1050 Brussels).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Paints Or Removers (AREA)

Abstract

A method for preparing an aqueous polyurethane dispersion, comprising (a) preparing a prepolymer with free NCO groups by reacting an aliphatic or cycloaliphatic polyisocyanate with a polyol, and an anionic compound; (b) dispersing said prepolymer in water; (c) reacting said water-dispersed prepolymer with a diamino hydrazide of the formula: <IMAGE> wherein R is an alkylene group of 2 to 15 carbon atoms or a cycloalkylene or arylene group of 6 to 15 carbon atoms as a chain lengthening agent; (d) reacting the prepolymer of step (c) in said dispersion with formaldehyde to effect crosslinking.

Description

Die Erfindung betrifft kaltvernetzende anionische PUR-Dispersionen, die sich zur Beschichtung von Oberflächen, Herstellung von Filmen, Dichtungsmassen und Lederzurichtungen eignen.The invention relates to cold-curing anionic PU dispersions which are suitable for coating surfaces, producing films, sealants and leather finishes.

Emulgatorfreie lonomer-Dispersionen auf Basis von Polyurethanen (PUR) haben sich in der Praxis bewährt. Ursache hierfür dürfte ihre hohe mechanische und chemische Stabilität, ihr außergewöhnliches Filmbildungsvermögen, ihre gute Haftung auf Oberflächen sowie ihre große Variabilität im Hinblick auf Zusammensetzung und gewünschte Eigenschaften sein.Emulsifier-free ionomer dispersions based on polyurethanes (PUR) have proven themselves in practice. The reason for this is likely to be their high mechanical and chemical stability, their exceptional film-forming ability, their good adhesion to surfaces and their great variability in terms of composition and desired properties.

Derartige PUR-Dispersionen werden üblicherweise so hergestellt: Aus einem Polyisocyanat und einem Polyol, das man in weniger als der stöchiometrischen Menge einsetzt, wird ein Prepolymer hergestellt. Dieses wird mit einer ionomeren Verbindung umgesetzt, welche dem Prepolymer selbstemulgierende Eigenschaften verleiht. Man stellt eine Dispersion her, führt eine Kettenverlängerung durch und entfernt das Lösemittel nach dem sogenannten « Aceton »-Verfahren (vgl. Die Angewandte Makromolekulare Chemie 98, 133-165 (1981).Such PU dispersions are usually produced in this way: a prepolymer is produced from a polyisocyanate and a polyol which is used in less than the stoichiometric amount. This is reacted with an ionomeric compound which gives the prepolymer self-emulsifying properties. A dispersion is prepared, chain extension is carried out and the solvent is removed by the so-called “acetone” method (cf. Die Angewandte Makromolekulare Chemie 98, 133-165 (1981).

Die restlichen freien NCO-Gruppen des Prepolymeren dienen zur Umsetzung mit einem Kettenverlängerungsmittel.The remaining free NCO groups of the prepolymer are used to react with a chain extender.

Ein solches Verfahren wird beispielsweise in der CA-A 837174 beschrieben. Die danach erhaltenen stark vernetzten Produkte sind jedoch weder in Lösemitteln löslich noch koagulieren sie zu einheitlichen Filmen (vgl. DE-B2624442).Such a method is described, for example, in CA-A 837174. However, the highly crosslinked products obtained thereafter are neither soluble in solvents nor do they coagulate into uniform films (cf. DE-B2624442).

Es ist auch bekannt, das erhaltene Prepolymer mit Polyisocyanaten umzusetzen (vgl. DE-A 32 33 605).It is also known to react the prepolymer obtained with polyisocyanates (cf. DE-A 32 33 605).

Nach dem Verfahren der DE-A3238169 werden lineare anionische Prepolymere mit Diaminen verlängert und anschließend mit einem Vernetzungsmittel, wie z. B. einem methoxymethylierten Melamin oder Harnstoff bei Temperaturen über 150 °C umgesetzt und vernetzt. Es findet somit keine Vernetzung bei Raumtemperatur statt. Diese ist aber erwünscht, da viele Substrate nicht thermostabil sind.According to the process of DE-A3238169 linear anionic prepolymers are extended with diamines and then with a crosslinking agent such as. B. a methoxymethylated melamine or urea at temperatures above 150 ° C and crosslinked. There is therefore no crosslinking at room temperature. However, this is desirable since many substrates are not thermally stable.

Die Dispersionen der zitierten deutschen Auslegeschrift 26 24 442 werden folgendermaßen erhalten : Zunächst wird ein Prepolymer hergestellt, das neben noch freien NCO-Gruppen auch anionische Salzgruppen besitzt und eine Viskosität von 50 bis 10 000 mPa · s aufweist. Dieses wird sodann mit Verbindungen umgesetzt, deren aktive Wasserstoffe mit den NCO-Gruppen schneller reagieren als Wasser. Als geeignete Verbindungen werden Ammoniak, primäre und sekundäre Amine, bevorzugt Diamine, Hydrazinderivate (Spalte 13, Zeile 35 ff.), Hydrazide von Dicarbonsäuren und Sulfonsäuren, wie beispielsweise Adipinsäuremono- und -dihydrazid (Spalte 14, Zeile 13 ff.), genannt. Eine im geringen Umfang stattfindende Umsetzung des NCO-Gruppen enthaltenden Prepolymeren mit Wasser ist erwünscht, wird doch angenommen, daß die gute Dispergierbarkeit der Produkte auf die Bildung von Harnstoffbindungen und Carbaminsäuresalzen zurückzuführen ist (vgl. Spalte 4, Zeile 16 ff.). Die Dispersionen gemäß DE-B 26 24 442 weisen jedoch den Nachteil auf, daß selbst bei Zusatz von Vernetzern bei Temperaturen unter 100 °C keine Lösemittelbeständigkeit erreicht werden kann.The dispersions of the German published specification 26 24 442 are obtained as follows: First, a prepolymer is produced which, in addition to free NCO groups, also has anionic salt groups and has a viscosity of 50 to 10,000 mPa · s. This is then reacted with compounds whose active hydrogens react faster with the NCO groups than water. Suitable compounds are ammonia, primary and secondary amines, preferably diamines, hydrazine derivatives (column 13, line 35 ff.), Hydrazides of dicarboxylic acids and sulfonic acids, such as, for example, adipic acid mono- and dihydrazide (column 14, line 13 ff.). A small amount of reaction of the prepolymer containing NCO groups with water is desirable, since it is assumed that the good dispersibility of the products is due to the formation of urea bonds and carbamic acid salts (see column 4, lines 16 ff.). However, the dispersions according to DE-B 26 24 442 have the disadvantage that even when crosslinking agents are added at temperatures below 100 ° C., no solvent resistance can be achieved.

Das Verfahren der DE-A 31 40 873 (entsprechend US-A 4 335 029) geht von höherfunktionellen anionischen lonomeren mit über Carbonsäurehydraziden eingebauten Hydrazidgruppen aus, die mit Formaldehyd (vgl. DE-A 18 07 072) zu reaktionsfähigen Methylolverbindungen umgesetzt werden. Der Vorteil dieses Verfahrens liegt darin, daß nach Koagulation bei Raumtemperatur eine Kondensationsreaktion über die Methylolhydrazidgruppen ablaufen kann. Nachteilig ist aber, daß man die Lösemittelresistenz nur dadurch erzielen kann, daß man von lonomeren ausgehen muß, deren Funktionalität größer als 2 ist und die damit zwangsläufig hochviskos sind. Die Dispergierung erfordert spezielle Dispergiereinrichtungen, die in der Lage sind, extrem hohe Scherkräfte zu überwinden. Infolge Inhomogenität führt dieses Verfahren zu Filmen mit gestörtem Verlauf (vgl. Vergleichsbeispiel A), erniedrigten Glanzwerten nach der Pigmentierung und einer erhöhten Anfälligkeit gegenüber Wasser und Alkalien. Es wäre wünschenswert, könnte man die Vernetzung im wesentlichen erst nach der Dispergierung durchführen.The process of DE-A 31 40 873 (corresponding to US Pat. No. 4,335,029) starts from higher-functional anionic ionomers with hydrazide groups incorporated via carboxylic acid hydrazides, which are reacted with formaldehyde (cf. DE - A 18 07 072) to form reactive methylol compounds. The advantage of this process is that after coagulation at room temperature, a condensation reaction can take place via the methylolhydrazide groups. However, it is disadvantageous that the solvent resistance can only be achieved by starting with ionomers whose functionality is greater than 2 and which are therefore inevitably highly viscous. The dispersion requires special dispersing devices that are able to overcome extremely high shear forces. As a result of inhomogeneity, this process leads to films with a disturbed course (cf. Comparative Example A), reduced gloss values after pigmentation and an increased susceptibility to water and alkalis. It would be desirable if the crosslinking could essentially only be carried out after the dispersion.

Es wurde jetzt gefunden, daß man durch Verwendung eines Diaminohydrazids der Formel I

Figure imgb0001
wobei R ein zweiwertiger aliphatischer Rest mit 2 bis 15 C-Atomen oder ein cycloaliphatischer oder aromatischer Rest mit jeweils 6 bis 16 C-Atomen ist, die aufgeführten Schwierigkeiten umgehen kann. Vorzugsweise wird ein Prepolymer mit linearem Molekülaufbau eingesetzt. Die mindestens 70 gewichtsprozentige Lösung des Prepolymeren sollte vorzugsweise eine maximale Viskosität von 10000 mPa . sec aufweisen. Die freien NCO-Gruppen des lonomeren werden mit den Aminogruppen des Diaminohydrazids kettenverlägert. Die endgültige Vernetzung erfolgt durch die an sich bekannte Reaktion zwischen Formaldehyd und den Hydrazidgruppen.It has now been found that by using a diaminohydrazide of the formula I
Figure imgb0001
 where R is a divalent aliphatic radical with 2 to 15 C atoms or a cycloaliphatic or aromatic radical with 6 to 16 C atoms each, can avoid the difficulties listed. A prepolymer with a linear molecular structure is preferably used. The at least 70 percent by weight solution of the prepolymer should preferably have a maximum viscosity of 10,000 mPa. have sec. The free NCO groups of the ionomer are chain-extended with the amino groups of the diaminohydrazide. The final crosslinking takes place through the reaction known per se between formaldehyde and the hydrazide groups.

Gegenstand dieser Erfindung sind daher die Verfahren zur Herstellung wäßriger PUR-Dispersionen gemäß den Ansprüchen 1 bis 3, die nach diesen Verfahren erhaltenen Dispersionen gemäß Anspruch 4 sowie die Verwendung der Dispersionen zur Herstellung von Filmen gemäß Anspruch 5.This invention therefore relates to the processes for the production of aqueous PUR dispersions according to claims 1 to 3, the dispersions obtained by these processes according to claim 4 and the use of the dispersions for the production of films according to claim 5.

Das erfindungsgemäße Verfahren beruht auf der Erkenntnis, daß Dicarbonsäurehydrazide, wie beispielsweise Adipinsäuredihydrazid, zur Vernetzung des Prepolymeren wenig geeignet sind. Eigene Untersuchungen ergaben, daß die Reaktivität der Hydrazidgruppen gegenüber den freien NCO-Gruppen eines nach Beispiel 4.1 erhaltenen lonomeren auf Basis von Isophorondiisocyanat so gering ist, daß die Umsetzung mit Wasser zu einer ernsten Nebenreaktion wird (vgl. Tabelle 1). Ähnliche Ergebnisse wurde mit lonomeren auf Basis anderer Isocyanate erhalten.The process according to the invention is based on the knowledge that dicarboxylic acid hydrazides, such as adipic acid dihydrazide, are not very suitable for crosslinking the prepolymer. Our own investigations showed that the reactivity of the hydrazide groups towards the free NCO groups of an ionomer based on isophorone diisocyanate obtained according to Example 4.1 is so low that the reaction with water becomes a serious side reaction (cf. Table 1). Similar results were obtained with ionomers based on other isocyanates.

Die Wasserreaktion ist unerwünscht, da sie keinen Beitrag zur Verzweigung leistet. Die Umsetzung des Prepolymeren mit einem Dihydrazid wirkt sich in diesem Sinne ebenfalls ungünstig aus. Aus statistischen Gründen kommt es nämlich nicht nur zu der gewünschten Umsetzung einer Hydrazidgruppe mit dem Prepolymeren ; vielmehr ist in erheblichem Umfang mit der Reaktion beider funktioneller Gruppen zu rechnen. Dies hat zur Folge, daß die Zahl der an dem Prepolymer gebundenen Hydrazidgruppen, die für die abschließende Vernetzung mit Formaldehyd zur Verfügung stehen, stark eingeschränkt ist.The water reaction is undesirable because it makes no contribution to branching. In this sense, the reaction of the prepolymer with a dihydrazide also has an unfavorable effect. For statistical reasons, it is not only the desired reaction of a hydrazide group with the prepolymer; rather, the reaction of both functional groups can be expected to a considerable extent. As a result, the number of hydrazide groups bound to the prepolymer, which are available for the final crosslinking with formaldehyde, is severely limited.

Setzt man jedoch ein Diaminohydrazid der Formel I ein, so kommt es - aufgrund der wesentlich höheren Reaktivität der Aminogruppe - zu einer selektiven Reaktion. Die Konkurrenzreaktionen werden auf ein Mindestmaß beschränkt. Diese Vorgehensweise ermöglicht es, von weniger vernetzten und damit leichter handhabbaren Prepolymeren auszugehen.However, if a diaminohydrazide of the formula I is used, a selective reaction occurs because of the substantially higher reactivity of the amino group. The competitive reactions are kept to a minimum. This procedure makes it possible to start from less crosslinked and therefore easier to handle prepolymers.

Das erfindungsgemäße Verfahren zeichnet sich durch folgende Vorteile aus :

  • 1. Es wird ein weniger vernetztes Prepolymeres hergestellt, das weniger viskos und damit rührbar und leichter handhabbar ist.
  • 2. Eine weitgehende Vernetzung wird erst nach der Koagulation der Dispersion erreicht.
  • 3. Man erhält harte, hoch vernetzte Filme mit verbesserter Lösemittelbeständigkeit.
The method according to the invention is characterized by the following advantages:
  • 1. A less crosslinked prepolymer is produced which is less viscous and therefore stirrable and easier to handle.
  • 2. Extensive crosslinking is only achieved after the dispersion has coagulated.
  • 3. Hard, highly cross-linked films with improved solvent resistance are obtained.

Im folgenden sollen die einzelnen Stufen des Verfahrens beschrieben werden ;The individual stages of the process are described below;

Zunächst wird ein Prepolymer aus einem Polyisocyanat, einem Polyol und einer anionischen Verbindung hergestellt. Als Lösemittel verwendet man vorzugsweise N-Methylpyrrolidon und/oder Aceton. Als Katalysator kann Dibutylzinndilaurat (DBTL) zugesetzt werden.First, a prepolymer is made from a polyisocyanate, a polyol and an anionic compound. The solvent used is preferably N-methylpyrrolidone and / or acetone. Dibutyltin dilaurate (DBTL) can be added as a catalyst.

Als Polyisocyanat werden eingesetzt :

  • 1. aliphatische oder cycloaliphatische Diisocyanate mit bis zu 15 C-Atomen. Bevorzugt sind cycloaliphatische Diisocyanate mit 6 bis 15 C-Atomen, insbesondere Isophorondiisocyanat (IPDI).
  • 2. Addukte der unter 1. aufgeführten Diisocyanate mit den weiter unten aufgeführten Polyolen, insbesondere Trimethylolpropan (TMP), sowie mit Melamin.
  • 3. Oligomere der unter 1. aufgeführten Diisocyanate, vorzugsweise die Isocyanurate.
The following are used as polyisocyanate:
  • 1. aliphatic or cycloaliphatic diisocyanates with up to 15 carbon atoms. Cycloaliphatic diisocyanates having 6 to 15 carbon atoms, in particular isophorone diisocyanate (IPDI), are preferred.
  • 2. Adducts of the diisocyanates listed under 1. with the polyols listed below, in particular trimethylolpropane (TMP), and with melamine.
  • 3. Oligomers of the diisocyanates listed under 1., preferably the isocyanurates.

Als Polyole werden folgende OH-Gruppen enthaltende Verbindungen mit Molekulargewichten zwischen 500 und 2 000 eingesetzt :

  • 1. Polyester, bestehend aus folgenden Säure- und Alkoholkomponenten : a) aliphatische und aromatische Dicarbonsäuren mit 5 bis 15 C-Atomen oder deren Anhydride, wie Adipinsäure, Decandicarbonsäure, Isophthalsäure und Phthalsäureanhydrid ; b) Polyole mit 2 bis 15 C-Atomen und 2 bis 4 OH-Gruppen pro Molekül, wie Ethylenglykol, Diethylenglykol, 1,4-Butandiol, Neopentylglykol, 1,6-Hexandiol, Trimethylolpropan (TMP) und Pentaerythrit.
  • 2. Lineare und trifunktionelle Polycaprolactone. Derartige Produkte erhält man ausgehend von difunktionellen Verbindungen, wie Wasser und Ethylenglykol, oder trifunktionellen Verbindungen wie TMP in Gegenwart von Zinnkatalysatoren bei Temperaturen bis 160 °C.
  • 3. Polyether auf Basis von Glykolen, wie Polypropylenglykol und Polytetramethylenglykol.
The following OH group-containing compounds with molecular weights between 500 and 2,000 are used as polyols:
  • 1. Polyester, consisting of the following acid and alcohol components: a) aliphatic and aromatic dicarboxylic acids having 5 to 15 carbon atoms or their anhydrides, such as adipic acid, decanedicarboxylic acid, isophthalic acid and phthalic anhydride; b) polyols with 2 to 15 carbon atoms and 2 to 4 OH groups per molecule, such as ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, trimethylolpropane (TMP) and pentaerythritol.
  • 2. Linear and trifunctional polycaprolactones. Such products are obtained from difunctional compounds such as water and ethylene glycol, or trifunctional compounds such as TMP in the presence of tin catalysts at temperatures up to 160 ° C.
  • 3. Polyethers based on glycols, such as polypropylene glycol and polytetramethylene glycol.

Als anionische Verbindungen werden Carbon- und Sulfonsäuren mit maximal 10 C-Atomen eingesetzt. Geeignet sind Diaminocarbonsäuren, Diaminosulfonsäuren und Dihydroxycarbonsäuren. Bevorzugt wird Dimethylolpropionsäure.Carbon and sulfonic acids with a maximum of 10 carbon atoms are used as anionic compounds. Diaminocarboxylic acids, diaminosulfonic acids and dihydroxycarboxylic acids are suitable. Dimethylolpropionic acid is preferred.

Anschließend werden die freien Säuregruppen des Prepolymeren durch Zugabe einer Base neutralisiert.The free acid groups of the prepolymer are then neutralized by adding a base.

Dies kann zum Beispiel ein Alkalihydroxid oder ein tertiäres Amin sein. Bevorzugt wird Triethylamin.This can be, for example, an alkali hydroxide or a tertiary amine. Triethylamine is preferred.

Das neutralisierte Prepolymer ist nicht lagerungsstabil. Es sollte daher bald weiterverarbeitet werden. Man erzeugt vorzugsweise die wäßrige Dispersion, indem man eine kräftige Rührgeschwindigkeit (ca. 100 Umdrehungen pro Minute) einstellt und die ein- bis dreifache Menge Wasser zusetzt.The neutralized prepolymer is not stable in storage. It should therefore be processed soon. The aqueous dispersion is preferably produced by setting a vigorous stirring speed (approx. 100 revolutions per minute) and adding one to three times the amount of water.

Sobald die Lösung homogen ist, läßt man vorzugsweise eine ca. 30 %ige wäßrige Lösung des Diaminohydrazids der Formel I unmittelbar in die entstandene Dispersion unter Rühren zügig einlaufen.As soon as the solution is homogeneous, an approximately 30% strength aqueous solution of the diaminohydrazide of the formula I is preferably rapidly run into the resulting dispersion with stirring.

Schließlich wird vorzugsweise bei einer Temperatur von etwa 45 °C eine verdünnte Formalinlösung zugegeben und bei dieser Temperatur etwa 30 Minuten bis zur vollständigen Methylolbildung umgesetzt.Finally, a dilute formalin solution is preferably added at a temperature of about 45 ° C. and the mixture is reacted at this temperature for about 30 minutes until the methylol has completely formed.

Das Diaminohydrazid I wird durch Umsetzung eines Diamins der Formel H2N-R-NH2 mit 0,2 bis 2 Mol eines Acrylsäurederivats, vorzugsweise Acrylsäureethylester, und nachfolgend mit Hydrazin erhalten.The diaminohydrazide I is obtained by reacting a diamine of the formula H 2 NR-NH 2 with 0.2 to 2 mol of an acrylic acid derivative, preferably ethyl acrylate, and subsequently with hydrazine.

Geeignete Diamine der Formel H2N-R-NH2 sind aliphatische Diamine mit 2 bis 15 C-Atomen oder cycloaliphatische oder aromatische Diamine mit jeweils 6 bis 15 C-Atomen, wie z. B. Ethylendiamin, Butandiamin-1,4, Hexamethylendiamin, 2,2,4- und 2,4,4-Trimethylhexamethylendiamin, 4,4'-Diaminodicyclohexylmethan und Xylylendiamin. Isophorondiamin wird bevorzugt.Suitable diamines of the formula H 2 NR-NH 2 are aliphatic diamines with 2 to 15 C atoms or cycloaliphatic or aromatic diamines each with 6 to 15 C atoms, such as. B. ethylenediamine, 1,4-butanediamine, hexamethylenediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, 4,4'-diaminodicyclohexylmethane and xylylenediamine. Isophoronediamine is preferred.

Die fertigen Dispersionen werden z. B. mit einem Rakel auf eine glatte Oberfläche (z. B. Glas oder Metall) aufgebracht. (Herstellung eines Diaminohydrazids als Kettenverlängerungsmittel)The finished dispersions are e.g. B. applied with a squeegee to a smooth surface (e.g. glass or metal). (Preparation of a diaminohydrazide as a chain extender)

170,0 g (1 Mol) Isophorondiamin werden in einem 1-1-Dreihalskolben, versehen mit Rührer, Rückflußkühler, Gaseinleitungsrohr und Tropftrichter, unter Stickstoff vorgelegt und unter Rühren auf 45°C vorgeheizt. 100,0 g (1 Mol) Acrylsäureethylester wird innerhalb von 90 Minuten bei einer Temperatur von 45 bis 50 °C unter Rühren eingetropft. Man hält den Ansatz anschließend weitere 7 Stunden unter mäßiger Rührung bei dieser Temperatur. Danach ist der Acrylester vollständig umgesetzt. Das Produkt hat einen Brechungsindex von nD 25 = 1,476 5. Anschließend werden 50,0 g (1 Mol) Hydrazinhydrat (N2H4 · H20) unter Rühren bei einer Temperatur von 50 °C zügig zugegeben. Dann wird die Mischung unter weiterem Rühren vorsichtig auf 65 °C etwärmt. Etwa bei 60 °C setzt die Reaktion unter milder Wärmeentwicklung ein. Nach 5 Stunden, wenn die anfängliche Trübung verschwunden ist, ist die Reaktion beendet.170.0 g (1 mol) of isophoronediamine are placed in a 1 liter three-necked flask equipped with a stirrer, reflux condenser, gas inlet tube and dropping funnel, under nitrogen and preheated to 45 ° C. with stirring. 100.0 g (1 mol) of ethyl acrylate is added dropwise within 90 minutes at a temperature of 45 to 50 ° C with stirring. The batch is then kept at this temperature for a further 7 hours with moderate stirring. The acrylic ester is then completely converted. The product has a refractive index of n D 25 = 1.476 5. 50.0 g (1 mol) of hydrazine hydrate (N 2 H 4 .H 2 0) are then added rapidly with stirring at a temperature of 50 ° C. Then the mixture is carefully warmed to 65 ° C. with further stirring. At around 60 ° C, the reaction begins with mild heat. After 5 hours, when the initial turbidity has disappeared, the reaction is complete.

Die Produktkontrolle erfolgt durch potentiometrische Titration. Mit Salzsäure in Isopropanol als Lösemittel werden die primären und sekundären Aminogruppen erfaßt.

  • Titration mit HCI : 6,28 mMol Amin/g
  • (6,25 berechnet)
The product is controlled by potentiometric titration. The primary and secondary amino groups are detected using hydrochloric acid in isopropanol as the solvent.
  • Titration with HCI: 6.28 mmol amine / g
  • (6.25 calculated)

Beispiel 2Example 2 (Allgemeine Beschreibung der Herstellung der Dispersion)(General description of the preparation of the dispersion)

In einem Dreihalskolben werden Dimethylolpropionsäure, gegebenenfalls Trimethylolpropan sowie N-Methylpyrrolidon und/oder Aceton vorgelegt und unter leichtem Rühren auf 60 °C erwärmt. Nun werden das Polyol und Dibutylzinndilaurat eingerührt. Die erforderliche Menge IPDI wird so zugegeben, daß die Reaktionstemperatur 80 °C nicht überschreitet. Nach etwa 5 Stunden Reaktionszeit, wenn die jeweilige theoretische NCO-Zahl erreicht ist, läßt man abkühlen. Man setzt Triethylamin zu, bis die Reaktionsmischung neutral reagiert, stellt eine Rührgeschwindigkeit von 100 Umdrehungen pro Minute ein und gibt das Wasser innerhalb von 1 Minute hinzu. Sobald sich eine homogene Lösung gebildet hat, wird eine 30%ige wäßrige Lösung des Hydrazids gemäß Beispiel 1 innerhalb von 1 Minute zugesetzt. Dabei ist darauf zu achten, daß die wäßrige Lösung möglichst ohne Berührung der Innenwand des Reaktionskolbens direkt in die entstandene Dispersion einfließen kann. Nach 5 Minuten wird die Rührgeschwindigkeit reduziert. Man hält die Reaktionslösung 2 Stunden bei 45 °C, setzt die 37 %ige wäßrige Formalinlösung zu und hält eine weitere Stunde bei 45°C. Nach Abkühlung wird die Reaktionslösung durch ein Filtertuch filtriert. Wird Aceton als Lösemittel verwendet, so wird es bei einer Temperatur von maximal 60 °C im Rotationsverdampfer unter vermindertem Druck abgezogen. Die erhaltenen Dispersionen haben einen Feststoffgehalt von etwa 30 Gewichtsprozent.Dimethylolpropionic acid, optionally trimethylolpropane and N-methylpyrrolidone and / or acetone are placed in a three-necked flask and heated to 60 ° C. with gentle stirring. Now the polyol and dibutyltin dilaurate are stirred in. The required amount of IPDI is added so that the reaction temperature does not exceed 80 ° C. After a reaction time of about 5 hours, when the respective theoretical NCO number has been reached, the mixture is allowed to cool. Triethylamine is added until the reaction mixture has a neutral reaction, the stirring speed is set at 100 revolutions per minute and the water is added within 1 minute. As soon as a homogeneous solution has formed, a 30% aqueous solution of the hydrazide according to Example 1 is added within 1 minute. It is important to ensure that the aqueous solution can flow directly into the resulting dispersion without touching the inner wall of the reaction flask. After 5 minutes the stirring speed is reduced. The reaction solution is kept at 45 ° C. for 2 hours, the 37% aqueous formalin solution is added and the mixture is kept at 45 ° C. for a further hour. After cooling, the reaction solution is filtered through a filter cloth. If acetone is used as the solvent, it is drawn off at a maximum temperature of 60 ° C. in a rotary evaporator under reduced pressure. The dispersions obtained have a solids content of about 30 percent by weight.

Beispiel 2.1Example 2.1

Mit anderen Diaminen wie Ethylendiamin, Hexamethylendiamin-1,6, 2-Methylpentamethylendiamin und 2,2,4- und/oder 2,4,4-Trimethylhexamethylendiamin wurden ähnliche Ergebnisse erhalten.Similar results were obtained with other diamines such as ethylenediamine, 1,6-hexamethylenediamine, 2-methylpentamethylenediamine and 2,2,4- and / or 2,4,4-trimethylhexamethylenediamine.

Beispiel 3Example 3 (Polyole)(Polyols) Beispiel 3.1Example 3.1

Aus 4 Mol Adipinsäure, 3 Mol Neopentylglykol und 2 Mol 1,6-Hexandiol wird ein linearer Polyester mit einer OH-Zahl von 110 hergestellt.A linear polyester with an OH number of 110 is prepared from 4 moles of adipic acid, 3 moles of neopentyl glycol and 2 moles of 1,6-hexanediol.

Beispiel 3.2Example 3.2

Es kommt ein Polytetramethylenglykol mit einem Molekulargewicht von 1 000 zum Einsatz. Ein solches Produkt ist unter dem Namen TERATHANE® 1 000 im Handel erhältlich (Hersteller Fa. E. I. du Pont de Nemours and Company, Wilmington, Del., USA).A polytetramethylene glycol with a molecular weight of 1,000 is used. Such a product is commercially available under the name TERATHANE® 1,000 (manufacturer E.I. du Pont de Nemours and Company, Wilmington, Del., USA).

Beispiel 3.3Example 3.3

Es kommt ein Polytetramethylenglykol mit einem Molekulargewicht von 2000 zum Einsatz. Ein solches Produkt ist unter dem Namen TERATHANE® 2000 im Handel erhältlich (Hersteller Fa. E. I. du Pont de Nemours and Company, Wilmington, Del., USA).A polytetramethylene glycol with a molecular weight of 2000 is used. Such a product is commercially available under the name TERATHANE® 2000 (manufacturer E.I. du Pont de Nemours and Company, Wilmington, Del., USA).

Beispiel 3.4Example 3.4

Es kommt ein Polycaprolacton mit einem Molekulargewicht von 2000 zum Einsatz. Ein solches Produkt ist unter dem Namen CAPA® 220 im Handel erhältlich (Hersteller Fa. Solvay & Cie., B-1050 Brüssel).

Figure imgb0002
Figure imgb0003
Figure imgb0004
 A polycaprolactone with a molecular weight of 2000 is used. Such a product is commercially available under the name CAPA® 220 (manufacturer Solvay & Cie., B-1050 Brussels).
Figure imgb0002
Figure imgb0003
Figure imgb0004

(analog zu DE-A 31 40 873(analogous to DE-A 31 40 873

375 g (0,5 Äquivalente) eines linearen Polyesters gemäß Beispiel 3.3, 33,6 g (0,8 Äquivalente) Melamin und 355,2 g (3,2 Äquivalente) Isophorondiisocyanat werden in Gegenwart von 0,05 Gewichtsprozent Dibutylzinndilaurat und 350 g N-Methylpyrrolidon bei 140 °C innerhalb von 3 Stunden zur Reaktion gebracht. Danach werden 53,6 g (0,8 Äquivalente) Dimethylolpropionsäure zugegeben und bei 80 °C solange umgesetzt, bis ein NCO-Gehalt von 3,5 Gewichtsprozent erreicht ist. Unter Einsatz eines hochwirksamen Dispergators wurde nun 327 g Wasser zugesetzt und sofort darauf mit 12 g (0,41 Äquivalenten) Ethylendiamin und 6,9 g (0,21 Äquivalente) Diethylentriamin kettenverlängert. Es wurde mit 69,5 g (0,81 Äquivalente) Adipinsäuredihydrazid überkappt und schließlich mit 32,5 g (0,41 Äquivalente) einer 37 %igen wäßrigen Formalinlösung in 30 g Wasser bei 45 °C 1 Stunde umgesetzt. Es entstand eine grobdisperse Dispersion, die nur wenige Tage mit starkem Bodensatz beständig war. Aus der Dispersion war nach Auftragen mit einem Rakel kein klarer einheitlicher Film zu erzielen.375 g (0.5 equivalents) of a linear polyester according to Example 3.3, 33.6 g (0.8 equivalents) of melamine and 355.2 g (3.2 equivalents) of isophorone diisocyanate are mixed in the presence of 0.05 percent by weight of dibutyltin dilaurate and 350 g N-methylpyrrolidone reacted at 140 ° C within 3 hours. 53.6 g (0.8 equivalents) of dimethylolpropionic acid are then added and the reaction is continued at 80 ° C. until an NCO content of 3.5 percent by weight is reached. Using a highly effective dispersant, 327 g of water were then added and the chain was immediately extended with 12 g (0.41 equivalents) of ethylenediamine and 6.9 g (0.21 equivalents) of diethylene triamine. It was capped with 69.5 g (0.81 equivalents) of adipic dihydrazide and finally reacted with 32.5 g (0.41 equivalents) of a 37% strength aqueous formalin solution in 30 g of water at 45 ° C. for 1 hour. The result was a coarsely disperse dispersion that was stable for only a few days with heavy sediment. A clear, uniform film could not be obtained from the dispersion after application with a doctor blade.

Vergleichsbeispiel BComparative Example B

Anstelle von 355,2 g Isophorondiisocyanat werden 428,8 g 4,4'-Methylenbis(cyclohexylisocyanat) eingesetzt. Die Lösung in N-Methylpyrrolidon war extrem viskos ; daher mußte Aceton als zusätzliches Verdünnungsmittel zugesetzt werden. Nach Zusatz der Formalinlösung konnte auch durch Verdünnung keine einheitliche Dispersion erhalten werden.Instead of 355.2 g of isophorone diisocyanate, 428.8 g of 4,4'-methylenebis (cyclohexyl isocyanate) are used. The solution in N-methylpyrrolidone was extremely viscous; therefore, acetone had to be added as an additional diluent. After adding the formalin solution, no uniform dispersion could be obtained even by dilution.

Claims (6)

1. A process for the production of an aqueous anionic PUR dispersion by
preparation of a prepolymer having NCO end groups and based on a (cyclo)aliphatic polyisocyanate, a polyol and an anionic compound,
its dispersion in water and
its reaction with a chain-extending agent having amino and hydrazine groups and with formaldehyde as a cross-linking agent, characterized in that a prepolymer is prepared by reacting a (cyclo)aliphatic polyisocyanate with a polyol (molecular weight from 500 to 2,000), a carboxylic or sulfonic acid having at most 10 carbon atoms and a base in an organic solvent, and prepolymer dispersed in water is first reacted with a diamino-hydrazide of the formula I,
Figure imgb0007
R being an aliphatic radical having 2 to 15 carbon atoms or a cycloaliphatic or aromatic radical each having 6 to 15 carbon atoms, and subsequently crosslinked with formaldehyde in a manner known per se.
2. A process according to claim 1, characterized in that the procedure in the first stage is such that a prepolymer solution of at least 70 % by weight solids content and a viscosity of at most 10,000 mPa - sec. is obtained, acetone or N-methylpyrrolidone being used as the solvent.
3. A process according to claim 1 or 2, characterized in that the radical R has the structure
Figure imgb0008
4. An anionic PUR dispersion based on a prepolymer containing urethane groups, a diamino-hydrazide of the formula I defined in claim 1 and formaldehyde, obtainable by a process according to any of claims 1 to 3.
5. The use of an aqueous anionic PUR dispersion produced according to any of claims 1 to 3 for the production of films.
EP85107926A 1984-08-24 1985-06-26 Cold-curable pur dispersions, their production and their use Expired EP0172362B1 (en)

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AT411998B (en) * 2002-01-02 2004-08-26 Surface Specialties Austria SURFACE PROTECTION FOR PAINTED SURFACES
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